Spreadable fats

ABSTRACT

A novel mixture of C8 and C10 glycerides in a specified crystalline form may be used in margarine and other fat compositions. The compositions may be used as the sole or principal fat in food spreads suitable for consumers whose ordinary fat metabolism may be impaired, as an additive to confer a marked cooling effect to conventional edible fat blends, and as a component in other fat compositions which is more resistant to the deterioration commonly met in unsaturated fats.

United States Patent Menz et al. 51 Apr. 25, 1972 [54] SPREADABLE FATS2,874,056 2/1959 Drew ..99/122x 2,914,546 11/1959 Barskyetal. ...99/122x[721 Invenwm Menz Hamburg-schenefeld; 3,006,771 10/1961 Babayan ..99/122Johannes Erich Rost, Hamburg; Theophil Wieske, Hamburg, all of GermanyLever Brothers Company, New York, NY.

Filed: Mar. 7, 1969 App1.No.: 805,352

Assignee:

Foreign Application Priority Data March 7, 1968 Germany ..P 16 92 541.0

References Cited UNITED STATES PATENTS 4/1941 Drew ..260/410.7

Primary Examiner-Joseph M. Golian Attorney-Louis F. Kline, Jr., MelvinH. Kurtz and Edgar E. Ruff [5 7] ABSTRACT sistant to the deteriorationcommonly met in unsaturated fats.

1 1 Claims, No Drawings SPREADABLE FATS This invention relates to fatcompositions. In particular the invention relates to fat compositionswhich are plastic and which contain or which may consist for their fatcomponents substantially entirely of medium chain triglycerides. Thesemay be defined as triglycerides of C and C saturated fatty acids, incontrast to the acids predominating in fats, which are not only ofgreater chain length but are often also unsaturated.

The present invention provides a fat composition comprising a mixture ofC and C 10 glycerides, including at least about 45 percent tricaprin, ofwhich a substantial, i.e., at least 20 percent of the mixture, part isin the B crystalline form.

In common with other glyceride fats, the medium chain triglycerides ofthe present invention can exist in three crystalline forms, a, B and B.The majority of these triglycerides in the a and B forms are liquid atroom temperature, for example even B tricaprin melts at 18 C. The Bcrystalline form of this component melts at 3 1 .5 C. however and maytherefore comprise part of a plastic fat composition.

A plastic fat composition is one which is spreadable at roomtemperature, i.e., between and 22 C. spreadability has been evaluatedwith reference to hardness measurements by Haighton, (Fette, Seifen,Anstrichmittel, 65, 479-482 1963)). According to this publication,hardness values below 100 g./cm refer to a very soft unstable product,and above 1,500 g./cm the product is too hard. The range 100-800 ispreferred for good spreadability, but 800-1500 is still acceptable.

The hardness measurements represent yield values determined by conepenetrometer as described in J.A. Oil CS. 36, 349 (1959), usually with acone weighing 80 g. with an angle of 40 C.

It is clearly necessary for spreadability to avoid the sharp meltingcharacterizing a pure compound and for this reason the compositions ofthe present invention contain at least one more C /C triglyceride inaddition to tricaprin. Preferably the C /C mixture contains 45-95percent tricaprin. In particular, the plastic fat compositions of theinvention contain at least 80 percent tricaprin and monocaprylodicaprin,and the major part of the crystalline form of the fat is not greaterthan g. This ensures that, over the range specified, the fat is aplastic. The particle size requirement also avoids a sandy taste for theedible plastic compositions of the invention.

A characteristic property of C lC glycerides is that they are absorbedby a different metabolic mechanism from that involved in the case ofhigher glycerides and they may therefore be prescribed to patients whosenormal fat metabolism is disturbed. The invention extends therefore toplastic edible spreads the fat content of which consists substantiallyentirely of the plastic C /C mixture, including margarine which may bespread in the normal manner. In addition, the invention includesemulsified spreads, for example, margarine, in which part or all thecustomary range of higher fats is replaced by the plastic mixture of Cand C glycerides as hereinbefore defined. In particular, the inventionincludes margarine fat compositions in which the plastic fat comprisingC and C glycerides predominates and is blended with a minor proportion,e.g., 5 percent of a vegetable oil the glycerides of which contain atleast percent polyunsaturated fatty acids. Margarine based on suchcompositions thus combines the dietetic advantage attributed to C /Cfats with that of such highly onsaturated constituents, at the same timeremaining spreadable and plastic at room temperatures, with 90 percentor more of the C /C fat.

The spreadability of the fat compositions of the invention which consistlargely or solely of C and C glycerides is surprising in view of thefact that hitherto fats with good spreadability have been characterizedby comparatively flat dilatation curves whereas these compositions ofthe invention have substantially steeper dilatation curves because ofthe relatively few distinct chemical entities which they contain incomparison with natural fats such as coconut or cocoa butter fats. Itwas unexpected, therefore, that the C and C glycerides alone could beobtained in a desirable consistency for spreading, even with highermelting points.

A further advantage of the compositions of the invention the fat contentof which consists substantially wholly of C and C glycerides is thatbeing all saturated, these glycerides are substantially more resistantto oxidation than natural fats containing unsaturated acids e.g., oleic,linoleic, and linolenic acids, while yet being obtained in plastic form.Where natural fats are hydrogenated sufficiently to stabilize the fat byremoving centers of unsaturation, the product may commonly be too hardto be incorporated in spreadable products in more than limited amounts.The invention therefore includes natural fat compositions of which onlypart is replaced by the plastic compositions of C and C glycerides. Inthis further function as additives to otherwise conventional fatcompositions the C /C glycerides are preferably present to at least 15percent. The compositions of which they form part may be intended fornon-edible use, e.g., in creams, ointments, suppositories, and otherconstituents and bases for cosmetic and pharmaceutical purposes.

Other compositions in which the mixtures of glycerides may be presentinclude films for packaging foils to reduce the adhesion between thepackaging material and the packaged contents and to minimisewater-permeability. They may also be present in solid solvents, e.g.,for phosphatides.

A particularly important application of the use as additives of themixtures of C and C glycerides according to the invention is however inedible fat compositions. C and C glyceride fat compositions of theinvention melt over a very narrow range, about 8 to 10 C.; they thusconfer a marked cooling" effect on the tongue, even in contact with itat room temperature, because of the rapid removal of the heat ofmelting. The compositions are therefore, particularly suitable asadditives, in relatively small amounts, to confer this effect onotherwise conventional edible fat products, e.g., margarine, filling forcream wafers, coating masses for baked goods and the like. Preferably atleast 15 percent of the additive is used, but 50 percent or more of theC lC solids may be present in spreadable products. It has been observed,for example, that 15 percent added to a margarine imparts as muchcooling effect as 30 percent of coconut oil, while giving betterconsistency and spreadability.

The amount of B crystalline form present in the mixture of C and Cglycerides is preferably at least 50 percent to maintain good plasticityover a wide range. The B form is the most stable and has the highestmelting point of the three crystalline forms. The [3 form is readilyobtained by effecting super-cooling of the molten mixture of C and Cglycerides, preferably to temperatures at least 12 C. and moreespecially at least 15 C. below the melting point of the mixture, andcontinuing crystallization preferably at higher temperatures. These maybe reached by warming the mixture to e.g., 12 to 22 C, according to thecomposition of the fat.

Where the mixture of C and C glycerides according to the invention isincorporated in foodstuffs, the mixture is preferably subjected tomechanical treatment to comminute a major part of the B form present toa particle size not greater than 20p. and preferably below 1541.. Thisfurther treatment, which may be carried out during crystallisation,ensures that sandiness in taste is avoided.

In the mixtures of C and C glycerides according to the inventionexcellent results have been obtained with weight values for the C :Cfatty acids of (25 to 5):(75 to 95) and more particularly from (15 to5):(85 to 95) and especially (13 to 10):(87 to The c,;c,., compositionmay be made up of glycerides in the fat which contain in the samemolecule other fatty acid residues.

Thus in compositions in which at least 90 percent consists of themixture of C and C glycerides, the remainder may consist to aconsiderable extent of edible compositions of glycerides ofpolyunsaturated fatty acids, particularly linoleic acid, which may alsocontain C and C acids in the same glyceride molecule. Preferably alsothe mixture contains at least 50 percent tricaprin and at least 80percent and preferably more than 85 percent is tricaprin andmonocaprylodiacaprin. The ratio of tricaprin to monocaprylodicaprin ispreferably (45 to 95):(40 to Preferably also, the combined content oftricaprylin and monocaprinodicaprylin is kept to 20 percent at most, andpreferably less than percent.

In addition to the glycerides described, which are triglycerides, thecompositions of the invention may also contain a proportion of C and Cdiglycerides. The amount which may be present is not critical, but ispreferably not more than and in particular is preferably 2 to 15percent, referred to the C and C glycerides. Preferably the overwhelmingproportion of diglyceride present is dicaprin.

By contrast preferably edible compositions of the invention containsubstantially no monoglycerides, since these have an undesirable tasteeffect and even in additive compositions the monoglyceride contentshould not exceed 0.1 percent. of C and C monoglycerides.

The invention may be more clearly understood by reference to theaccompanying Examples.

EXAMPLE 1 963 g. of capric acid (99.5 percent) and 145 g. of caprylicacid (99.5 percent) were esterified with 188 g. of 99 percent glycerol(90 percent of theory) with the addition of 1.22 g. of caustic soda ascatalyst. During the esterification, a pressure of 20-25 mm Hg wasmaintained, and the temperature of the mixture was initially 150 C. andwas raised gradually to 195 C. After 24 hours, the esterification wasended at an acid number of 20.8, and the product was deacidified with a10 percent excess of 2 N caustic soda solution at 90 C. washed withwater, and post-deacidified with 0.2 N caustic soda solu- EXAMPLE 2 Amargarine the fat phase of which consisted of 95 percent of glyceridesof C and C fatty acids and 5 percent of sunflower seed oil was made inessentially the same manner as in Example 1. The fat composition was asfollows:

Tricaprin 55.1% Monocaprylodicaprin 28.3% Dicaprylomonocaprin 5.8%Tricaprylin 0.4% C and C diglycerides 5.4% Subtotal: 95.0% Sunflowerseed oil 5.0% Total: 100.0%

The B phase content of the C /C mixture was more than 50 percent and theparticle size of the crystals was below 10 The margarine had similardesirable properties to the margarine prepared according to Example 1.

A series of trials was carried out on various fat compositions preparedand incorporated in an emulsion similar to those described in Example 1.The particulars of the compositions are set out in Table l, in which thehardness values are C values at 15 C. in g/cm according to I-Iaighton'spublication. In all the trials the monoglyceride content of the sampleswas less than 0.1 percent.

TABLE I Composition, wt. percent Hardness at Tricaprin plus 15 Particlemonocaprylo- M,P,, size 1 Tricaprin dicaprin Diglyceride 0, Before Afterafter At 22 C,

tion. The fat was washed to neutrality with hot water, dried for 30 min.at 95 C. in vacuum with stirring, and subsequently bleached with 5percent of bleaching earth for 30 min. under the same conditions. Thefat was filtered and heated with 30 percent of water for 6 hours at 180C. and 5 mm Hg in a laboratory steamer.

In the final product (about 970 g.), monoglycerides could no longer bedetected by thin-layer chromatography, and the content of diglycerides(by GLC) was 6 percent. The content of tricaprin was 55.6 percent andthat of monocaprylodicaprin 31.5 percent. The remaining 6.9 percentconsisted of 6.5 percent of dicaprylomonocaprin and 0.4 percent oftricaprylin. The acid number was 0.04. The melting point on heating was23.5 C.

To make a margarine, after the addition of 0.2 percent of defattedalcohol-soluble soya phosphatide fraction and 0.2 percent of a mixtureof monoand diglycerides from hardened palm oil, 240 g. (80 percent) ofthis fat was melted at 37 C. and emulsified in the Hobart mixer with 20percent of an aqueous phase, which consisted of 30 g. of skim milksoured by lactic acid fermentation and 30 g. of water. The emulsion wascooled to below +10 C. and stirred, whereupon the fat crystallized.After crystallization was complete, the margarine was homogenized in ahomogenizing machine (Gann-Emulgor, setting 4) at about 18 C. threetimes, whereupon more Comparing the emulsified products of these trials,the first was fully liquid. In trial 2 the product contained less thanpercent tricaprin, in the fat phase but samples based on the fat beforecomminution could be spread, although some sandiness in taste wasobserved. The composition could be used, for example in ointments andcreams for non-edible purposes.

As the total content of tricaprin and monocaprylodicaprin is increased,the product hardens, as shown by trial 3, so that after comminution itwas satisfactory in a spreadable product. It was less satisfactory as anadditive in about 15 percent to conventional margarine fats, although itwas cool-tasting, because in comminuted form it was very soft at higherroom temperatures. The comminuted product of trial 4 fulfils all thepreferred requirements according to the invention for a fat suitable foruse as the sole fat in a margarine fat or as an additive to conventionalmargarines. Margarines based solely on this product could be easilyspread and showed no sandiness. A small amount of the comminuted productadded to conventional margarine fat conferred remarkable coolnesswithout sandiness.

The product of trial 5 contained too much tricaprin to be entirelysatisfactory as the sole fat in margarine, and was not sufficiently softat lower room temperatures. The hardness value was in fact measured at22 C. because at 15 C. the fat was too hard for an accurate measurementto be made. Where as in trial 6 the product was solely tricaprin, theproduct was a crystalline powder which could not be spread even athigher room temperatures, above which eventually it melted sharply.Trial 7 was carried out to illustrate the effect of high diglyceridecontent upon the product. The composition was prepared byinteresterification of a mixture of C and C triglycerides containing 65percent tricaprin and 26 percent monocaprylodicaprin with 2 percentglycerol in the presence of sodium methoxide as catalyst. Theinteresterified mixture was washed with water to remove catalyst anddried.

Although the melting points of diglycerides are higher than those ofcorresponding triglycerides, a high diglyceride content is seen in trial7 to depress the melting point of the fat to the point where it isplastic only in the lower ranges of room temperatures.

What is claimed is:

1. A mixture of glycerides of saturated C and C fatty acids consistingessentially of:

i. tricaprin, and

ii. monocaprylodicaprin, said tricaprin being present in the amount of45 percent to 95 percent by weight of said mixture, the total oftricaprin and monocaprylodicaprin being at least 80 percent by weight ofsaid mixture, the ratio of tricaprin to monocaprylodicaprin being 45 to95 parts by weight of tricaprin to 40 to five parts by weight ofmonocaprylodicaprin, at least 20 percent of said mixture of glyceridesbeing in the beta crystal form, said mixture of glycerides containingsubstantially no monoglycerides, and not more than 20 percent of C and Cdiglycerides.

2. Mixture of glycerides according to claim 1 wherein at least 50percent of said mixture is in beta crystal form.

3. Mixture of glycerides according to claim 1 wherein the ratio of fattyacids combined as residues is 13-10 parts of C fatty acids to 87-90parts of C fatty acids.

4. Mixture of glycerides according to claim 1 wherein the particle sizeof the major part of the beta crystals is not greater than 20microns.

5. An edible plastic fat composition suitable for use as the sole fat inthe formulation of a margarine fat consisting essentially of the mixtureof glycerides of claim 25 and a vegetable oil the glycerides of whichcontain at least 40% polyunsaturated fatty acids, the proportion of saidmixture of glycerides of claim 25 being at least 90 percent of saidcomposition, the remainder consisting of said vegetable oil.

6. An edible plastic fat composition in accordance with claim 5 whereinsaid vegetable oil is sunflower oil.

7. Process for the preparation of a plastic fat composition as claimedin claim 4 which comprises supercooling said mixture of C and Cglycerides to a temperature of at least 12 C below its melting point,crystallizing said mixture until at least 20 percent thereof is presentin the beta crystalline form and comminuting said crystallized mixtureuntil the size of the major part of said beta crystals is not greaterthan 20 microns.

8. Process according to claim 7 wherein said mixture is crystallized ata temperature of 12 to 22 C.

9. A margarine consisting essentially of about percent of a fat phaseand about 20 percent of an aqueous phase, wherein said fat phasecomprises the mixture of glycerides of claim 4.

10. A margarine consisting essentially of about 80% of a fat phase andabout 20% of an aqueous phase, wherein said fat phase comprises thecomposition of claim 5.

11. A margarine in accordance with claim 9 wherein said fat phasecomprises Tricaprin 5 5.1% Dicaprylomonocaprin 5.8% Monocaprylodicaprin28.3% Tricaprylin 0.4% C and C diglycerides 5.4% Sunflower seed oil 5.0%

Total: 100.0%

2. Mixture of glycerides according to claim 1 wherein at least 50percent of said mixture is in beta crystal form.
 3. Mixture ofglycerides according to claim 1 wherein the ratio of fatty acidscombined as residues is 13-10 parts of C8 fatty acids to 87-90 parts ofC10 fatty acids.
 4. Mixture of glycerides according to claim 1 whereinthe particle size of the major part of The beta crystals is not greaterthan 20microns.
 5. An edible plastic fat composition suitable for use asthe sole fat in the formulation of a margarine fat consistingessentially of the mixture of glycerides of claim 25 and a vegetable oilthe glycerides of which contain at least 40% polyunsaturated fattyacids, the proportion of said mixture of glycerides of claim 25 being atleast 90 percent of said composition, the remainder consisting of saidvegetable oil.
 6. An edible plastic fat composition in accordance withclaim 5 wherein said vegetable oil is sunflower oil.
 7. Process for thepreparation of a plastic fat composition as claimed in claim 4 whichcomprises supercooling said mixture of C8 and C10 glycerides to atemperature of at least 12* C below its melting point, crystallizingsaid mixture until at least 20 percent thereof is present in the betacrystalline form and comminuting said crystallized mixture until thesize of the major part of said beta crystals is not greater than 20microns.
 8. Process according to claim 7 wherein said mixture iscrystallized at a temperature of 12* to 22* C.
 9. A margarine consistingessentially of about 80 percent of a fat phase and about 20 percent ofan aqueous phase, wherein said fat phase comprises the mixture ofglycerides of claim
 4. 10. A margarine consisting essentially of about80% of a fat phase and about 20% of an aqueous phase, wherein said fatphase comprises the composition of claim
 5. 11. A margarine inaccordance with claim 9 wherein said fat phase comprises Tricaprin 55.1%Dicaprylomonocaprin 5.8% Monocaprylodicaprin 28.3% Tricaprylin 0.4% C8and C10 diglycerides 5.4% Sunflower seed oil 5.0% Total: 100.0%